the use of dra in crude oil - coqa-inc. · pdf filethe use of dra in crude oil coqa meeting...

© 2009 Baker Hughes Incorporated. All Rights Reserved.

The Use of DRA in Crude OilCOQA MeetingJune 10, 2010

David SchwartzBaker Hughes

Preview

• Background• Crude quality and DRA

–Key challenges –DRA chemistry and product composition–DRA fate testing

• Summary and Conclusions

(DRA is a “Drag Reducing Agent”)

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Benefits of Drag Reducers

• Increased throughput– Without capital expenditure (new pumps, lines, etc.)– Allows pipelines to meet their scheduled nominations

• Energy savings– Cheaper than horsepower…can shut down pump stations

• Scheduling flexibility– Increases slow (or fast) component of line batches

• Derated periods– Maintain desired throughput at reduced MAOP– Maintain throughput during scheduled maintenance


Effect of DRA• DRA dissolves in the pipeline liquid• DRA decreases turbulent flow and increases laminar flow• DRA does not coat the pipeline wall

Without Without DRADRA

TurbulentTurbulentCoreCore

With With DRADRA

BufferBufferZoneZone

LaminarLaminarSublayerSublayer

Chemistry of Drag Reducers• DRA active ingredient

– Ultra-high molecular weight, linear poly-alpha-olefin– 100% hydrocarbon, ultra high MW, completely saturated

• DRA product types– Gel

• Older technology, polymer “dissolved” in a hydrocarbon solvent

– Slurry• Typically water-based• Freeze-protected versions also contain alcohol and/or glycol ether• Typically much higher performance than the gel products, and easier

to handle


xR R R

DRA Product Composition


Product type Polymer (%) Carrier(s) (%) Other Ingredients

Gel Polyolefin (10%)

Kerosene, pentane (90%)

None

Water-based slurry

Polyolefin (20-30%)

Water (60-75%)

Stabilizing agents (up to 5%)

Freeze-protected slurry

Polyolefin (20-30%)

Alcohol, glycol, glycol ether (10-75%)

Stabilizing agents (up to 5%)

Typical percentage composition ranges shown

Crude Oil Quality and DRA—Key Challenges

•Refinery process differences– Straight run cuts vs hydrotreated; product slate; etc.

•Complexity of the DRA additive– Some DRA’s have 5 or more components– How low do you go? 1% of DRA, 0.1%, lower??

•Refiners’ perception of DRA risk vs reward•Our direct customers are pipeline companies•Any process impact could be small/slow


Crude Oil Quality and DRA--History• DRA additives first used in crude oil in 1979, on the trans-

Alaskan pipeline system

• Around that time, we did the following work :– Impact testing at two refineries

• Process condition changes, product specs, trace metals levels

– Lab testing examining desalter impact, foaming tendency and acidnumber

• Since that time, DRA has been used to treat over 100 billion barrels of crude, all around the world

• No major problems tied to DRA


Who Uses DRA in Crude Oil

Shell ExxonMobilPEMEX EnbridgeAlyeskaMarathon


BPMaersk Saudi AramcoIOCL YPFSinclairSunoco

PERN SUMEDCEPEKOCKTOCPCBTC

DRA Fate Testing• Desalter

– Octanol/water partition coefficient (Log Pow)– EDDA– COD/BOD

• Refined product quality– TGA– Pyrolysis GC-MS– Spec testing on cut (spiked with DRA component(s) or distilled

from DRA-containing crude)

• Process impact– All of the above– Elemental analysis– Chemical and process knowledge


Testing for the Presence of DRA

• It’s relatively easy to test a refined fuel sample for DRA

– Polymer—GPC, NMR, filterability– Carriers—GC/MS– Stabilizing agents—IR, GC/MS, etc.

• Not so easy for a crude sample, due to the crude’s complex composition


DRA Polymer Fate


Polymer degrades at 400 C

TGA

DRA Polymer Fate Testing


Polymer degrades to its monomers (alpha-olefins), at 400 C

Peaks C and G are monomers

GC-MS

DRA Component Fate in a Refinery


Component Level in crude

Expected fate

Polymer 20 ppm VDU bottoms, then similar to other non-volatile, saturated hydrocarbons

Alcohol 30 ppm Distills in ADU, based on boiling point

Stabilizing agent(s) 5 ppm Varies

Assume a crude contains100 ppm of a freeze-protected DRA additive (20% polymer, 45% water, 30% alcohol, 5% stabilizing agents):

Typically, the polymer and carrier(s) will not be water soluble

Summary and Conclusions• DRA has been used in crude oil for over 30 years, over 100 billion barrels have been treated

• DRA additives provide significant benefits to crude producers, transporters, refiners and end users

• There are several real challenges in the area of DRA and crude quality

• We want to work with you to address any concerns you might have with respect to DRA


Thank you

Questions?


Supporting Information Follows


Slurry DRA Stabilizing Agents

• A slurry stabilizing agent package must be “tri-functional”– Partitioning (prevent agglomeration)– Wetting (prevent liquid/solid separation)– Rheology (slow down rate of separation)

• Typical slurry stabilizing agents– Metal stearates, sulfates, phosphates– Polyolefin waxes– Organic stearamides– Clays– Fatty acid waxes– Silica


EDDA Testing with FLO MXA


Sample Dose Rate (ppm)BPR27140

Water Drop WQ Interface

5’ 10’15’

20’ 25’ 30’ GN/A

Light crude(no DRA additive)

0 0.5 0.60.6

0.6 0.6 0.6G

N/A

10 0.2 0.40.5

0.6 0.8 0.8G

N/A

30 0.6 0.9 1.5 2 2.2 3 G- GLC w/ additive 0 9 9 9 9 9 9 G G

10 9 9 9 9 9 9 G- G30 9 9 9 9 9 9 G- G

Heavy crude no additive 0 1.5 2.2 2.8 3 4 4 G G-

10 3.5 5 6 6 7 8 G G-

30 4.5 5.5 6.5 7 8 8 G G-

HC w/additive 0 3 3.5 3.5 4 5 5 G G-

10 3.5 5 5. 6 6 7 G G-

30 4 5.5 5.5 6 7 7 G G-

Sample 0 % Water %

BS

% Total % Slug

LC –no additive 0 1.2 1.2 0.6 (plug) no water

LC w/ additive Tr 0.4 0.4 0.4

HC no additive 0.1 0.6 0.6 0.2/0.4 (0.2% plug)

HC w/additive 0 0.4 0.4 0.2

Initial BS&W

DRA and Refined Fuel Product Quality

•EPA registration as a fuel additive•Sulfur and metals levels•Impact on fuel’s spec. properties

– Corrosivity, filter plugging, cloud point, gums, etc.•Engine testing•Behavior in biofuels

– Diesel/biodiesel blends– Ethanol/gasoline blends


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